JPS6291561A - High-molecular stabilizer compound - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a production method and a stabilized polymer composition comprising an organic polymer and the above solid polymeric stabilizer compound.

It is known that organic polymers (such as polystyrene, polyolefins and polydienes) are degraded by exposure to the atmosphere, especially by the action of ultraviolet radiation. Due to this deterioration, it is common practice to incorporate small amounts of stabilizer compounds, generally phenols or sterically hindered amines, into organic polymers to alleviate such deterioration of the polymer. For example, derivatives of pyrrolidine (U.S. Pat. Nos. 4,325,864 and 4,346,188) and derivatives of tetramethylmorpholine or pentamethylmorpholine (European Patent Publication No. 115 , No. 055) is known.

Problems in stabilizing organic polymers stem from the incompatibility between the organic polymer and the stabilizer and the release of the stabilizer by the polymer. When stabilizing using conventional stabilizers, the above-mentioned disadvantages occur to varying degrees. Therefore, there is an increasing need for compounds that are compatible with organic polymers and can be stably retained within the polymers.

One solution to this problem is patent application No. 10921 (1986).
It is disclosed in No. 2. The specification of this application describes stabilizer compounds containing a sterically hindered amine group and a hydrolyzable silicic acid function in the same molecule. These stabilizer compounds correspond to silicic acid functional groups and either hydrolyze or interact with inorganic solid supports containing superficial hydroxyl groups or organic polymers with ethylenically unsaturated bonds; They also produce complex structures that remain more stable within the introduced organic polymer than do conventional sterically hindered amines.

However, stabilizer compounds containing a sterically hindered amine group and a silicic acid functional group in the same molecule have poor reactivity toward supports, particularly polymeric supports, and as a result, stabilizers with high loadings on such supports. It was observed that it was difficult to bind the agent. Moreover, the complex structures described in such patent applications are not always completely satisfactory with respect to the properties of homogeneity and compatibility with organic polymers.

SUMMARY OF THE INVENTION It is therefore an object of the present invention to overcome the above-mentioned drawbacks of the known technology.

The present invention provides that a product obtained by introducing a metal atom into an organic polymer having a hydrogen atom that can be replaced by a metal atom (a hydrogen atom that can be replaced by a metal atom) has a reactive electrophilic functional group in its molecule. It is based on the concept that it reacts easily with sterically hindered amine compounds containing groups, and the solid and finely divided products formed from this reaction are easily homogenized with organic polymers. be.

Thus, it has physical properties that can be easily homogenized with organic polymers and, on the one hand, retains unchanged the stabilizer properties characteristic of sterically hindered amines, but on the other hand, it has a high degree of compatibility within organic polymers. It is possible to simply and easily produce a solid polymeric stabilizer compound containing a desired amount of active nitrogen that exhibits and durability properties.

Therefore, the solid polymeric stabilizer compound according to the invention is
A group containing a sterically hindered amine functional group (sterically hindered amine functional group-containing group) is bonded to an organic polymer matrix. - an aromatic, heteroatom-containing aromatic, diene or olefinic polymer matrix, in which sterically hindered amine functional group-containing groups replace at least some of the metal-displaceable hydrogen atoms of said matrix; The polymeric stabilizer compound has a molecular weight of about 1,000 to about 100,000 and an active nitrogen content of at least 0.14% by weight.

A preferred method for preparing solid polymeric stabilizer compounds according to the present invention involves the following sequence of steps.

a) dissolving a vinyl-aromatic, hetero-atom-containing aromatic, diene-based or olefin-based polymer containing a metal atom-substitutable hydrogen atom in an inert organic solvent; b) the vinyl-aromatic, hetero a step of at least partially replacing the metal-atom-substitutable hydrogen atoms of the atom-containing aromatic, diene-based or olefin-based polymer with metal atoms via reaction with a metal-introducing agent; C) as described above; A vinyl-aromatic, heteroatom-containing aromatic, diene or olefin polymer into which a metal atom has been introduced is combined with a sterically hindered amine functional group and an electrophilic functional group.
In particular, by reacting with compounds containing carbonyl functional groups,
d) separating said polymeric stabilizer compound as a finely divided solid from the reaction mixture of said step.

Another method for the preparation of solid polymeric stabilizer compounds according to the invention is according to the living polymer technique, in the presence of a lithium alkyl catalyst and a vinyl-aromatic and/or
Alternatively, diene monomers are polymerized, and the metal atom-containing polymer thus obtained is then reacted with a compound containing a sterically hindered amine functional group and an electrophilic functional group (particularly a carbonyl functional group). It is something that makes you

Such products are also considered stabilized polymer compositions.

The stabilized polymeric composition of the present invention comprises an organic polymer and an amount of the solid polymeric stabilizer compound such that the active nitrogen content in the composition is at least 0.005% by weight. Become.

Organic lightning complexes into which metal atoms are introduced that are suitable for the purpose of the present invention are described in A. J. Chalk et al., Journal of Polymer Science (J. Polym, 5ci).
JA-1.

7, 691 (1969), J. C. Brusse
[Makromol,
Chem, ) J 183.2193 (1982),
D. P. Tate et al. [Journal of Polymer Science J A-1, 9, 139 (1971) and A. J. Amass et al. [Journal of European Polymers (Bur, Polym, J.)
J8, 781 (1972), vinyl-aromatic, heteroatom-containing aromatic, diene or olefinic compounds containing hydrogen atoms that can be replaced by metal atoms.

Typical (but not limited to) polymers into which metal atoms can be introduced include polymethylstyrene (
For example, poly-p-methylstyrene), poly-2,6-
dimethyl-1,4-phenylene ether, polybutadiene, polyisoprene and ethylene/propylene/diene terpolymers (e.g. ethylene/propylene/ethylidene-norbornene terpolymers), styrene-butadiene copolymers, vinyl-aromatics, Random or block copolymers of diene or olefinic monomers and other types of monomers, such as alkyl-vinyl ethers (
For example, a copolymer between p-methylstyrene and octadecyl-vinyl ether).

These polymers have molecular weights comparable to those of the solid polymeric stabilizers used in their preparation. Alternatively, it is necessary to take into account the fact that molecular weight degradation often occurs during the introduction of metal atoms.

Metal atom introduction agents suitable for the purposes of the invention are metal alkyls (Cr C+t) , metal hydrides or metal amides of alkali metals, in particular sodium, lithium or potassium. Examples of such metal atom introducing agents include Li −
n-butyl, Li-secondary butyl, Na-amyl, Na
-cumyl, K-cumyl, Li-diisopropylamide,
There is NaH.

These metal introduction agents are typical activators for metal introduction reactions,
For example, it is used in combination with N,N,N',N'-tetramethylethylenediamine, potassium tertiary butoxide and diazobicyclooctane.

According to a preferred method of the invention, a solution of the polymer into which the metal is to be introduced in an inert organic solvent is first prepared.

Organic solvents suitable for this purpose are liquid aliphatic, cycloaliphatic or aromatic hydrocarbons (eg cyclohexane and toluene) and liquid ethers, especially cyclic ethers (eg tetrahydrofuran).

The metal atom introduction reaction is carried out by bringing the polymer into which the metal atom is to be introduced and the selected metal atom introduction agent into contact in an organic solvent, if possible with the addition of an activator for the metal atom introduction agent. The reaction is carried out at a temperature of 0 to 150°C, preferably 40 to 80°C, and a reaction time of generally 10 minutes to 6 hours.

The ratio of metal atom introduction agent to organic polymer is varied depending on the desired degree of metal atom introduction. However, 0.1 to 1.0 moles of the metal atom-introducing agent are usually used for each monomer unit of the polymer containing metal-substitutable hydrogen atoms used for such purposes.

By operating under the conditions described above, metal incorporation rates of 30 to 90% are generally achieved, calculated with respect to the metal atom introduction agent used.

As a metal introduction agent, lithium alkyl alone or in combination with the above activator, or lithium alkyl (lithium alkyl/activator molar ratio = 110.1 to 1/10, preferably l
10.5 to 1/1) gives best results.

For example, poly-p-methylstyrene H3 is used as a polymer containing hydrogen atoms that can be replaced by metal atoms, and lithium alkyl is used in the presence of the activator N, N, N', N'-tetramethylethylenediamine. When carrying out the metal atom introduction reaction, the general formula CH2Li C)13 (where m+p=ns m/p ratio is
metal atom-containing poly-p
-Methylstyrene is obtained.

Although the functional groups containing hydrogen atoms replaced by metal atoms are randomly distributed in the polymer chain, the above formula is used for simplicity. There is also a possibility, albeit small, of introducing a metal atom at the -(, R- group of the aromatic ring and/or styrene chain).

In any case, it is clear that the degree of substitution of hydrogen by metal atoms in compounds containing replaceable hydrogen atoms may be varied over a wide range simply by varying the ratio between the reactants.

Sterically hindered amine compounds useful for the purpose of the present invention include:
In the molecule, 2,2.6.6-tetramethylpiperidine $ 2.2,6.6-tetramethylmorpholine 2.2,5.
5-tetramethylpyrrolidine 1.3,3,5.5-pentamethylpiperazine H3 or other compounds containing a sterically hindered amine group H or in which the hydrogen bonded to the nitrogen atom is substituted with an alkyl group having 1 to 18 carbon atoms Some contain residues of derivatives such as

In addition to the above-mentioned amine groups, the compounds useful for the purposes of the invention also contain electrophilic functional groups necessary for reaction with polymers in which some hydrogen atoms have been replaced with metal atoms. For this purpose, various electrophilic functional groups can be used, with carbonyl groups being particularly suitable.

Thus, a particularly preferred compound is 2.2.6.6-tetramethyl-4-piperidone, which is readily obtained by reaction of acetone and ammonia.

Other suitable compounds include 3,3,5.5-tetramethylmorpholin-2-one, 1,3,3°5.5-pentamethylpiperazin-2-one, 2°2.5.5-one, Tetramethylimidazolin-4-one, t,a,a-trimethyldecahydroquinoxalin-2-one.

According to the method of the present invention, a polymer in which some hydrogen atoms have been replaced by metal atoms, which is contained in the solution from the metal atom introduction step, is further added to a sterically hindered amine compound containing an electrophilic functional group. bring into contact with. This reaction occurs when the ratio between the amine compound and the carbanion center of the polymer, in which some hydrogen atoms have been replaced by metal atoms, is stoichiometric or nearly stoichiometric, and the temperature is O The polymeric stabilizer compound of the present invention is produced under conditions in which the temperature ranges from 150° C. to 150° C. and the reaction time ranges from 30 minutes to 6 hours.

A suitable reaction temperature is about 40-80'C. The reaction yield is of the order of 60-99%, calculated on the aminated compound introduced under the experimental conditions employed.

In particular, by reacting poly-p-methylstyrene in which some hydrogen atoms have been replaced with metal atoms with 2,2,6,6-tetramethyl-4-piperidone, ) is obtained, in which the above-mentioned structure coexists with another structure (2), as shown by measuring the nitrogen content and by the 'HNMR spectrum.

The spectrum of poly-p-methylstyrene shows a gentle signal at δ1.35.1.85.2.25 in the aliphatic region, and a gentle signal at δ6.5.6.85 in the aromatic region.

The spectrum of the copolymer also clearly shows the presence of a signal at δ 1.1 due to the methyl group of 2,2,6,6-tetramethyl-4-piperidone.

The polymeric stabilizer thus obtained is precipitated by adding a non-solvent such as an alcohol (e.g. methanol), followed by filtering or centrifuging the solid, washing and drying. separated from the reaction mixture.

By operating as described above, it is possible to obtain a solid polymeric stabilizer that can be easily homogenized simply by mixing with the powder of the organic polymer whose stabilization is desired.

These solid polymeric stabilizers are further characterized by extremely high thermal stability and compatibility with very large organic polymers, especially
(If this organic polymer has the same properties as the polymer containing hydrogen that can be replaced with a metal atom, which was used to prepare the polymeric stabilizer). Finally, the solid polymeric stabilizer according to the present invention has the following characteristics, as is clear from the examples below.
They show little tendency to be extracted from the organic polymers with which they are blended.

As mentioned above, the solid polymeric stabilizer according to the present invention is
Living polymer technology involves polymerizing vinyl-aromatic and/or diene monomers (e.g. styrene and butadiene) in the presence of lithium alkyls to produce polymers in which some hydrogens have been replaced by metal atoms. generate,
It is also prepared by subsequently reacting this polymer with a sterically hindered amine compound having an electrophilic group.

Such products are also considered stabilized polymer compositions.

In the Examples, several examples of such operating methods will be reported.

The solid polymeric stabilizer according to the invention usually has an active nitrogen content of 0.14 to 5.4% by weight, which content is greater than the metal-substitutable hydrogen content polymer used in the synthesis. It is adjusted by various methods depending on the degree of metal atom introduction. The molecular weight of the stabilizer preferably ranges from about 1,000 to about so,ooo.

Thus, the stabilizer properties are best exhibited when two special requirements are met, namely solubility in the stabilizer preparation step and when the average molecular weight of the stabilizer is lower than the average molecular weight of the organic polymer to be stabilized. be considered.

According to the solid polymeric stabilizer of the present invention, polyolefins, polydiolefins, copolymers of monoolefins and diolefins, polystyrene, copolymers of dienes and vinyl aromatic monomers, polyphenylene oxides, etc. , polyphenylene sulfide, polyurethane, polyamide and copolyamide, polyurea, polyimide and polyamide
It is also possible to stabilize compounds such as imides, polyesters, polycarbonates, polysulfones and polyethersulfones, unsaturated polyesters, organic polymers such as natural polymers (rubbers) and lubricating oils.

Thus, according to another aspect of the invention, a stabilized polymeric composition comprising an organic polymer and an amount of said solid polymeric stabilizer capable of functioning as a stabilizer is provided. It also relates to "The amount that can function as a stabilizer" means the amount of active nitrogen in the composition from 0.005 to 0.02% by weight,
Preferably 0. Q1 means the amount to ensure about 15% by weight. "Active nitrogen" means nitrogen supplied by a sterically hindered amine.

According to embodiments of the invention, these stabilizing polymers.

In the composition, the average molecular weight of the solid polymeric stabilizer is lower than the average molecular weight of the organic polymer.

The stabilized polymer compositions of the present invention are also prepared by any of the known techniques used to homogenize organic polymers with stabilizers. In a preferred embodiment, this is accomplished by simply mixing the organic polymer powder and the solid polymeric stabilizer powder.

The following examples are intended to illustrate the present invention, and include:
This is not intended to limit the invention.

Example! Cyclohexane 360xe, poly-p-methylstyrene (weight average molecular weight Mw = 14.500 Number average molecular weight Mn = H, 500, Mw/Mn = 1.07) 1
09 and heated to a temperature of 60°C to dissolve poly-p-methylstyrene in the solvent.
N,N by contacting for about 10 minutes at 25°C).

N', N'-tetramethylethylenediamine approx. 4
40 mmol (2!m2 of 1.6 M hexane solution) of Li-n-butyl reacted with Limol (←→g) was added.

The reaction was carried out at 60° C. for about 2 hours under a nitrogen atmosphere while stirring the reaction mass. After this time had elapsed, an aliquot (approximately 1/10) of the reaction mixture was removed and reacted with trimethylchlorosilane in order to detect the degree of metal atom introduction. The results showed that about 1 metal atom was incorporated per 5 monomer units of poly-p-methylstyrene. To equilibrate the reaction mixture, 2.8 g of 2,2,6,6-tetramethyl-4-piperidone was added to
- in an amount stoichiometrically equivalent to the carbanion center occurring in methylstyrene).

The mixture was stirred at a temperature of 60° C. for about 30 minutes, then methanol was added to precipitate the powdery solid, and the resulting precipitate was separated and dried under reduced pressure.

Elemental analysis of this solid confirmed the presence of approximately 1% by weight nitrogen, and in accordance with this data, NMR analysis revealed approximately 1 piperidine functional group per 10 monomer units comprising poly-p-methylstyrene. It was confirmed that these were bound together.

Example 2 The operation was carried out in the same manner as in Example 1 by dissolving polyphenylene oxide (molecular weight approximately 15,000) 109 in tetrahydrofuran to prepare a 2% by weight polymer solution.

To this solution was added Li-n-butyl (1,6 M solution in cyclohexane 521Q, i.e. about 1
molar amount) was added. The mixture thus obtained was stirred for 1 hour at a temperature of 20° C. under a nitrogen atmosphere. Then 2,2,6,6-tetramethyl-4-piperidone (8,79, i.e. the already charged Li-n-
(equivalent to about 70 mol % based on the number of moles of butyl) and the mixture was stirred at room temperature (20-25 °C) under a nitrogen atmosphere.
The mixture was stirred for several hours. Furthermore, methanol was added to the reaction mixture to precipitate a powdery solid, which was separated and dried.

Analysis showed that this solid had 0.7 piperidine units attached per monomer unit of polyphenylene oxide.

Example 3 The procedure was carried out in the same manner as in Example 1 by dissolving 6.49 g of polyisoprene (molecular weight approximately 20,000) in 200 m+2 cyclohexane.

Then, about 46 mmol of Li-secondary butyl (28.8 M (1") of a 1,6 M cyclohexane solution) was added together with 23 mmol (2,67 g) of N,N,N',N'-tetramethylethylenediamine, and the mixture was stirred. 2.6.6-Tetramethyl-4-piperidone 1 in a nitrogen atmosphere while
8.4 mmol (2,11159) were added. Contacting was carried out for an additional approximately 10 minutes under the conditions described above, and the solvent was removed under reduced pressure to yield a residual solid product. After purification by redissolving in cyclohexane and crystallizing with methanol, the product showed approximately 0.15 units of piperidone bound per unit of isoprene.

Example 4 In the same manner as in Example 1, in cyclohexane 200 pass,
Ethylene containing 5% by weight of ethylidene norbornene
Propylene-ethylidene norbornene terpolymer 109
The operation was carried out by dissolving. Next, L
i-n-butyl/ni-0-tertiary butyl mixture (1/1
Molar ratio) 4.2 mmol was added and the reaction was carried out at 70°C for 3 hours. The reaction was then continued for 60 minutes.

0.544% by weight of nitrogen by crystallization with methanol
A gummy solid product containing .

Examples 5-8 In place of piperidone in Example 1, the following compounds were used in the same amounts.

a) 3,3,5,5-tetramethylmorpholine-2
-one b) 1,3,3,5.5-pentamethylpiperazin-2-one c) 2,2,5,5. -Tetramethylimidazolin-4-one4) 1.3.3-Trimethyldecahydroquinoxalin-2-one reaction gives a solid, which is composed of poly-p-
It was shown that on average there is one nitrogen functionality per lO monomer unit of methylstyrene.

Example 9 5 g of styrene was mixed with 4.8 mmol of Li-secondary butyl (L, SM cyclohexane solution 31
1Q).

After this time had elapsed, 4.5 ml of 2,2,6,6-tetramethyl-4-piperidone (90,79) was added to the polymerization mixture, and the mixture was allowed to react at a temperature of 60° C. for about 1 hour.

Crystallization with methanol was carried out to separate a finely divided solid product. The product contained an amount of nitrogen equivalent to 1 unit of piperidone per 10 unit of styrene.

Example 10 The reactor described in Example 1 was charged with cyclohexane 400x &
129 styrene and 1.5 mmol of Li-sec-butyl were charged. The polymerization reaction was carried out at 60°C for 2 hours.

Then, butadiene 289 was introduced into the reaction mixture, and the mixture was reacted at the same temperature of 60° C. for 2 hours, after which 0.7 mmol of 2,6-distyrylpyridine (cyclohexane solution) was introduced.

The coupling reaction was completed in several minutes (approximately 10 minutes), and the resulting living polymer was reacted with 1.4 mmol (0.229) of 2,2,6,6-tetramethyl-4-piperidone. .

After about 80 minutes, the polymer was coagulated and purified by redissolving in toluene and crystallizing with methanol,
Dry. Product 409 was obtained with a bound stabilizer content of 0.5% by weight. According to NMR analysis, this product has a styrene unit content of about 30% by weight, and according to GPC analysis, it has a content of several. It showed an average molecular weight Mn of about 65,000.

Example 11 A p-methylstyrene-octadecyl vinyl ether copolymer 59 having a molecular weight of about 10.000 and containing 30% p-methylstyrene was mixed with 20O of anhydrous cyclohexane.
Dissolved in xff.

Li-n-butyl-N, prepared in advance by reacting the solution thus obtained at room temperature,
13 mmol of N,N',N'-tetramethylethylenediamine complex were added. The reaction was carried out at 60°C for 2 hours.

Anhydrous tetrahydrofuran 5RC was then added and after a few minutes crystallization was carried out with 2,2,6,6-tetramethylpiperidin-4-onhumi9 to isolate the solid product.

This product has an amine compound content of 13% by weight.

Example 12 a) Solid polymeric stabilizer (POL) obtained in Example I
-AO-1) was subjected to thermogravimetric analysis at a programmed temperature (10° C./min) under an inert gas atmosphere. The table below shows the weight loss of POL-AO-1 at various temperature ranges under the trade name TINUVIN 770 and CH IMA.
Comparison of the values obtained using a commercially available stabilizer known in SSORB944. Nao, TINUVIN 7
7G is a product of CIBA-GEIGY and has screws (2
, 2, 6, 6 products consisting of sterically hindered amines in polymeric form.

Table TlN0VIN770 1.3 20.1
1G0.0CHIMASSORB944 0.3
0.3 14.5POL-AO-
10,10,16,8 As is clear from the above table, stabilizer 1'0L-AO-1
is stable at high temperatures, and this property allows it to remain stable in polymeric compositions without breaking down or undergoing transformation phenomena within the temperature range at which the polymeric compositions are normally processed. It is particularly effective as a sex stabilizer.

Similar stability properties were observed for the solid polymeric stabilizers obtained in other Examples.

b) The effectiveness of POL-^0-1 as a stabilizer is also evidenced by its ability to prevent the degradation of polystyrene when exposed to UV radiation.

The introduction of the stabilizer into the polystyrene takes place in a powder mixing device. For example, MontedisonCon
Polystyrene commercially available from Cern (weight average molecular weight Mv = 234.Goo, number average molecular weight Mn = 5
5.000. My/Mn ratio=4.25) powder was homogenized with POL-AO-1 stabilizer powder in an amount such that the content of active nitrogen in the resulting composition was 0.015% by weight.

The resulting composition was heated to 135°C and a pressure of 900°C. /cm”
Press molding was performed for 2 minutes to obtain a film with a thickness of 50 μm. The film removed from the mold was rapidly cooled under running water and then subjected to alternating cycles of irradiation with a fluorescent lamp rich in UV radiation in the range 280 to 350 nm in a UVCON apparatus from ATLAS - condensation in the dark at a controlled temperature. It was subjected to an accelerated aging test. More specifically, during the test, irradiation was at 60°C for 8 hours and condensation was at 40°C for 4 hours. The deterioration of polystyrene was confirmed by the formation of carbonyl compounds (confirmed by IR spectrum) (C
Checked based on O index class. In particular, the increase in absorption at CO index class 1710 cm-' was measured as a function. In this test, l) polystyrene film without stabilizer, 2) stabilizer 1'0L-AO
3) a polystyrene film prepared in the same manner as above and containing commercially available (7) TINOVIN 770 in an amount giving an active nitrogen content of 0.015% by weight, at a time interval of 100 hours. The increase in absorption at 1710 cm-' was measured.

In the case of polystyrene film l) without additives, the CO index class increase was approximately 0.2, and for the other two films no formation of carbonyl bonds was observed within the time tested. Similar behavior was observed when using the solid polymeric stabilizers of Examples 5-8.

C) The compatibility of the stabilizer POL-AO-1 with polystyrene and the durability of the stabilizer in polystyrene under conditions of high thermal stress can be determined by the stability of the nitroxy groups obtained by the oxidation of the sterically hindered amine groups of the stabilizer molecule. Measuring the state concentration (for polymer samples containing stabilizers,
This was checked by ESR spectroscopy carried out at 170° C. for several hours. In particular, the formation of nitroxy groups is directly induced in polystyrene films by photooxidation with doublet oxygen. The polystyrene film was prepared as described above.

The amount of stabilizer POL-AO-1 is 2.5% by weight, corresponding to 0.015% by weight of active nitrogen. Photosensitizer (Ros
eBengal, chlorophyll) is 0.0% to the polymer.
It is added in an amount of 1% by weight. ESR spectroscopy using high pressure mercury vapor combined with a UV 31 filter (for irradiation at 290 nm) revealed the formation of groups and the temperature 170 nm.
A check was made on the durability of the stabilizer in the samples at °C.

The results of this test are reported in the charts of the accompanying drawings. The chart plots the base concentration (as a percentage of the initial concentration) on the vertical axis and time (time) on the horizontal axis. For comparison, commercially available stabilizer T [N0VIN 7
A graph obtained for a film made of the same polystyrene containing 7G in an amount such that the active nitrogen content is Q, 015% is also shown. In the chart, the symbol (△) indicates the result of the test according to the invention, and the symbol (.) indicates the result of the comparative test.

Similar results were observed using the solid polymeric stabilizers of Examples 5-8.

d) The polystyrene film containing the stabilizer POL-AO-1 obtained as described above was subjected to an extraction test (60°C
, carried out in 24 hours). Virtually no extraction of stabilizer from the polymer film was observed.

[Brief explanation of drawings]

The drawings show the results of tests conducted to evaluate the compatibility of the stabilizer of the present invention with polystyrene and the durability within the polymer, compared to the conventional stabilizer (and one other person).

Claims (1)

[Scope of Claims] 1. A solid polymeric stabilizer compound formed by bonding a group containing a sterically hindered amine functional group to an organic polymer matrix, wherein the organic polymer matrix contains hydrogen atoms capable of replacing metal atoms. a vinyl-aromatic, heteroatom-containing aromatic, diene, or olefinic polymer matrix containing sterically hindered amine functional groups, wherein the groups containing sterically hindered amine functional groups at least partially replace metal-displaceable hydrogen atoms of the matrix. and the polymeric stabilizer has a molecular weight of about 1000 to about 100,000 and an active nitrogen content of at least 0.005% by weight.
Polymeric stabilizer compound. 2. The product according to claim 1, wherein the organic polymer matrix is polymethylstyrene, poly-
2,6-dimethyl-1,4-phenyl ether, polybutadiene, polyisoprene, ethylene/propylene/diene terpolymer, styrene/butadiene copolymer, or vinyl-aromatic, diene, or olefin monomer and an alkyl-vinyl ether, wherein the sterically hindered amine functional group-containing group is 2,2,6,6-tetramethylpiperidine, 2,2,6,6- Tetramethylmorpholine, 2,2,5,5-tetramethylpyrrolidine, 2,2
, 3,5,5-pentamethylpyrrolidine, 2,2,5,
5-tetramethylimidazoline, 1,3,3,5,5-
A polymeric stabilizer compound derived from pentamethylpiperazine and 1,3,3-trimethyldecahydroquinoxaline. 3. A polymeric stabilizer compound according to claim 2, wherein the polymer matrix is a matrix comprising poly-p-methylstyrene. 4. A polymeric stabilizer compound according to claim 1, having an active nitrogen content of 0.14 to 5.4% by weight. 5. A method for producing a polymeric stabilizer compound in which a group containing a sterically hindered amine functional group is bonded to an organic polymer matrix, comprising: a) a vinyl-aromatic, heteroatom-containing compound containing a hydrogen atom capable of replacing a metal atom; dissolving an aromatic, diene, or olefin polymer in an inert organic solvent; b) replacing hydrogen atoms with metal atoms in the vinyl-aromatic, heteroatom-containing aromatic, diene, or olefin polymer; c) sterically hindered the vinyl-aromatic, heteroatom-containing aromatic, diene-based or olefin-based polymer into which the metal atoms have been introduced; reacting with a compound having an amine functional group and an electrophilic functional group to produce a polymeric stabilizer compound; d) converting the produced polymeric stabilizer compound from the reaction mixture of step c) into a finely divided solid; A method for producing a polymeric stabilizer compound, characterized in that: 6. In the manufacturing method according to claim 5, in step a), the hydrogen atom-containing polymer suitable for substitution with metal atoms is polymethylstyrene, poly-2,6
- dimethyl-1,4-phenylene ether, polybutadiene, polyisoprene, ethylene/propylene/diene terpolymer, styrene/butadiene copolymer and vinyl-aromatic, diene or olefinic monomer and alkyl-vinyl ether A polymer selected from random copolymers and block copolymers of Method for producing sex stabilizer compounds. 7. In the manufacturing method according to claim 5, in step b), a metal alkyl (C_1-C_1_2), an alkali metal hydride, or an alkali metal amide is used as the metal atom introduction agent, and the metal introduction reaction is carried out by: temperature 0
to 150°C, for 30 minutes to 6 hours, and in an amount of 0.1 to 1 mole of the metal-introducing agent per each monomer unit of the metal-substituted hydrogen atom-containing polymer.
Method for producing polymeric stabilizer compounds. 8. In the method according to claim 7, in step b), an activator selected from N, N, N', N'-tetramethylethylenediamine, potassium tertiary butoxide, and diazobicyclooctane. , the molar ratio of the metal atom introduction agent/activator is 1/0.1 to 1/1.
A method for producing a polymeric stabilizer compound in which the reaction is carried out by coexisting in an amount of 0, preferably 1/0.5 to 1/1. 9. The method for producing a polymeric stabilizer compound according to claim 7, wherein the metal atom-introducing agent is lithium alkyl. 10. A method for producing a polymeric stabilizer compound according to claim 7, wherein the reaction is carried out at a temperature of 40 to 80°C. 11 In the manufacturing method according to claim 5, in step c), in addition to the electrophilic functional group, especially the carbonyl group, 2,2,6,6-tetramethylpiperidine, 2
, 2,6,6-tetramethylmorpholine, 2,2,5,
5-tetramethylpyrrolidine, 2,2,3,5,5-pentamethylpyrrolidine, 2,2,5,5-tetramethylimidazoline, 1,3,3,5,5-pentamethylpiperazine or 1,3, using a sterically hindered amine compound containing a residue of 3-trimethyldecahydroquinoxaline,
The ratio of the amine compound to the carbanion center of the metal atom-containing polymer is stoichiometric or nearly stoichiometric, the temperature is 0 to 150°C, and the reaction time is 30 minutes to 6 hours. A method for producing polymeric stabilizer compounds that performs a reaction by operating under certain conditions. 12 In the manufacturing method according to claim 11, in the step c), 2,2,6,6-tetramethyl-
4-piperidone, 3,3,5,5-tetramethylmorpholin-2-one, 1,3,3,5,5-pentamethylpiperazin-2-one, 2,2,5,5-tetramethylimidazoline- A method for producing a polymeric stabilizer compound using an amine compound selected from 4-one and 1,3,3-trimethyldecahydroquinolin-2-one. 13. A method for producing a polymeric stabilizer compound according to claim 11, wherein in step c), the reaction is carried out at a temperature of 40 to 80°C. 14. The method for producing a polymeric stabilizer compound according to claim 5, wherein in step d), the polymeric stabilizer compound is separated by crystallization by adding a non-solvent. 15. The method for producing a polymeric stabilizer compound according to claim 14, wherein the non-solvent is an alcohol, particularly methanol. 16 In a method for producing a polymeric stabilizer compound in which a group containing a sterically hindered functional group is bonded to an organic polymer matrix, by polymerizing vinyl and/or diene monomers in the presence of a lithium alkyl catalyst. A polymeric stabilizer characterized by preparing a metal atom-containing polymer and reacting the obtained metal atom-containing polymer with a compound having a sterically hindered amine functional group and an electrophilic group, especially a carbonyl group. Method of manufacturing compounds. 17 Organic polymer and claims 1 to 4
and the solid polymeric stabilizer compound described in 1.
5 to 0.02% by weight, and the stabilizing polymer is characterized in that the polymeric stabilizer compound has an average molecular weight smaller than the average molecular weight of the organic polymer. Composition. 18. The stabilized polymer composition of claim 17, wherein the active nitrogen content is on the order of 0.015% by weight. 19 The product according to claim 17, wherein the organic polymer is a polyolefin, a polydiolefin,
Copolymers of monoolefins and diolefins, polystyrene, copolymers of dienes and vinyl aromatic monomers, polyphenylene oxides, polyphenylene sulfides,
polyurethanes, polyamides and copolyamides, polyureas, polyimides and polyamide-imides, polyesters,
Stabilized polymer compositions selected among polycarbonates, polysulfones and polyether-sulfones, unsaturated polyesters and natural polymers (rubbers).